Photosensitive resin composition, photosensitive resin film, photosensitive dry film, pattern formation method, and light-emitting element

Abstract

To provide a photosensitive resin composition which enables easy formation of a film having high lithography resolution and good light-emission characteristics, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition and a pattern formation method using them, and a light-emitting element obtained using the photosensitive resin composition.SOLUTION: A photosensitive resin composition contains (A) a silicone resin having a phenolic hydroxyl group, (B) a photo-acid generator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film using the photosensitive resin composition, a photosensitive dry film, a pattern forming method, and a light-emitting device. [Background technology]

[0002] Various methods have been proposed to create displays with red, green and blue subpixels. One method involves converting the light from an LED array from shorter wavelengths, blue, to longer wavelengths, red and green, through a color conversion structure, using quantum dots.

[0003] In recent years, LED arrays have become micro-sized, and micro LED displays using these have been attracting attention. One method for forming a color conversion structure on an LED array is a lithography process using a photosensitive material (Patent Document 1), but in recent years, further miniaturization is required for application to small displays. In addition, there are high demands for light emission characteristics in terms of display clarity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-089347 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition capable of easily forming a film having high lithography resolution and good light-emitting properties, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition, and a pattern forming method using these, as well as a light-emitting element obtained using the photosensitive resin composition. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides a photosensitive resin composition, comprising: (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) Quantum dots The quantum dots have a surface coating layer containing siloxane.

[0007] Such a photosensitive resin composition can easily form a film having high lithography resolution and good light emitting properties.

[0008] In the present invention, the component (C) preferably contains a skeleton having a phenolic hydroxyl group in the surface coating layer.

[0009] Such a photosensitive resin composition can prevent the quantum dots from escaping during development, and can provide a pattern with high light-emitting properties.

[0010] In the present invention, the component (A) preferably contains a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1). [ka] [In the formula, R 5 ~R 8 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 0 to 600. X 1 is a divalent group represented by the following formula (X1). [ka] (In the formula, Y 1R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 9 and R 10 R is each independently a hydrogen atom or a methyl group. 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 are each independently an integer of 0 to 7. 1 and b 2 are each independently an integer of 0 to 2.)]

[0011] If such a photosensitive resin composition is used, the resulting cured film will have high reliability.

[0012] In the present invention, it is preferable that the component (D) further contains at least one crosslinking agent selected from the group consisting of melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups per molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups per molecule.

[0013] Such a photosensitive resin composition can further increase the strength of the resin film after photocuring.

[0014] In the present invention, it is preferable that the quantum dots of the component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion.

[0015] Quantum dots having such ligands are preferred because they are easily coordinated to the surface.

[0016] In the present invention, the photosensitive resin composition preferably contains the component (C) in an amount of 5 to 80% by mass.

[0017] Such a photosensitive resin composition makes it possible to form a fine pattern while maintaining good light emitting properties.

[0018] In the present invention, it is preferable that the composition further contains a solvent (E).

[0019] Such a photosensitive resin composition can improve the coatability.

[0020] The present invention also provides a photosensitive resin film which is a dried product of the above-described photosensitive resin composition.

[0021] Such a photosensitive resin film has high lithography resolution and good light emitting properties.

[0022] The present invention also provides a photosensitive dry film comprising a support film and the above-described photosensitive resin film on the support film.

[0023] Such a photosensitive dry film has high lithography resolution and good light emitting properties.

[0024] The present invention also provides a pattern forming method, comprising the steps of: (i) applying the above-described photosensitive resin composition onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. The present invention provides a pattern forming method comprising the steps of:

[0025] The present invention also provides a pattern forming method, comprising the steps of: (i') attaching the photosensitive resin film of the photosensitive dry film described above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. The present invention provides a pattern forming method comprising the steps of:

[0026] These pattern formation methods make it possible to form patterns with high lithographic resolution, and to obtain film patterns having good light-emitting properties.

[0027] The present invention also provides a light-emitting device comprising a cured coating obtained by the above-described pattern formation method.

[0028] Such a light emitting element has high lithography resolution and good light emitting characteristics. Effect of the Invention

[0029] The photosensitive resin composition of the present invention contains a silicone resin having a phenolic hydroxyl group, a photoacid generator, and quantum dots having a specific surface coating layer, and therefore can easily form a coating having high resolution and good light-emitting properties, making it suitable for light-emitting devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] As described above, there has been a demand for the development of a photosensitive resin composition capable of easily forming a film having high lithography resolution and good light-emitting properties, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition, a pattern forming method using these, and a light-emitting element obtained using the photosensitive resin composition.

[0031] As a result of extensive investigations into the above-mentioned problems, the present inventors have discovered that a photosensitive resin composition comprising (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane, has high lithography resolution and can easily form a film (photosensitive resin film) having good luminescence properties, thereby completing the present invention.

[0032] That is, the present invention is a photosensitive resin composition, (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane.

[0033] The present invention will be described in detail below, but the present invention is not limited thereto.

[0034] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) a quantum dot having a specific surface coating layer. If necessary, it may further contain other components such as (D) a crosslinking agent and (E) a solvent. Each component constituting the photosensitive resin composition will be described below.

[0035] [(A) Silicone resin having a phenolic hydroxyl group] The (A) silicone resin having a phenolic hydroxyl group used in the present invention is not particularly limited as long as it has a phenolic hydroxyl group.

[0036] A preferred example is a silicone resin containing a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1). [ka]

[0037] In formula (a1), R 5 ~R 8 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include linear, branched or cyclic alkyl groups and aryl groups, specific examples of which include methyl, ethyl, propyl, hexyl and structural isomers thereof, cyclohexyl and phenyl groups. Of these, methyl and phenyl groups are preferred because of the ease of availability of raw materials.

[0038] In formula (a1), m is an integer of 0 to 600, preferably 0 to 400, and more preferably 0 to 200.

[0039] X 1 is a divalent group represented by the following formula (X1). [ka]

[0040] In formula (X1), Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 9 and R 10 R is each independently a hydrogen atom or a methyl group. 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 are each independently an integer of 0 to 7, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. 1 and b 2 are each independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0041] The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, structural isomers thereof, etc. The alkoxy group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, structural isomers thereof, etc.

[0042] Resin (A) contains repeating units such that a1+b1=1, with a1>0, and preferably 0.1≦a1≦0.9, 0.1≦b1≦0.9. Furthermore, the silicone content is preferably 20 to 80% by weight, and preferably 30 to 70% by weight.

[0043] (A) The silicone resin having a phenolic hydroxyl group provides film-forming ability, and the phenolic hydroxyl group functions as a photocrosslinking point.

[0044] The repeating units may be bonded randomly or as a block polymer. The siloxane units in each repeating unit may be bonded randomly or may contain a plurality of blocks of the same type of siloxane units. In the silicone resin (A) having a phenolic hydroxyl group, the silicone (siloxane unit) content is preferably 30 to 80 mass%.

[0045] The weight average molecular weight (Mw) of the (A) silicone resin having a phenolic hydroxyl group is preferably 3,000 to 500,000, and more preferably 5,000 to 200,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0046] The (A) silicone resin having a phenolic hydroxyl group is preferably produced by addition polymerization of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) in the presence of a metal catalyst.

[0047] [ka] (In the formula, R 5 ~R 8 and m are the same as above. [ka] (In the formula, R 9 ~R 12 , Y 1 , a 1 , a 2 , b 1 , b 2 is the same as above.)

[0048] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, as described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0049] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 mass % and more preferably 0.01 to 0.1 mass % in terms of platinum group metal, based on the total mass of compounds other than the solvent used in the addition polymerization reaction.

[0050] In the addition polymerization reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable.

[0051] The reaction temperature is preferably 40 to 150°C, more preferably 60 to 120°C, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time. The polymerization time depends on the type and amount of the resin obtained, but is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours, in order to prevent the intrusion of moisture into the polymerization system. After the reaction is completed, if a solvent is used, it can be distilled off to obtain (A) a silicone resin having a phenolic hydroxyl group.

[0052] In the present invention, the (A) silicone resin having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0053] [(B) Photoacid generator] The photoacid generator (B) is not particularly limited as long as it is decomposed by light irradiation and generates an acid, but it is preferable that it generates an acid by irradiation with light having a wavelength of 190 to 500 nm. (B) Photoacid generator is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0054] The onium salt includes a sulfonium salt represented by the following formula (B1) or an iodonium salt represented by the following formula (B2). [ka]

[0055] In formulas (B1) and (B2), R 101 ~R 105 are each independently an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0056] The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. The aryl group includes phenyl, naphthyl, and biphenylyl. The aralkyl group includes benzyl and phenethyl.

[0057] Examples of the substituent include an oxo group, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms.

[0058] R 101 ~R 105Preferred examples of the aryl group include an alkyl group which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, or a 2-oxocyclohexyl group; an aryl group which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, an m-, or p-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and an aralkyl group which may have a substituent such as a benzyl group or a phenethyl group. Of these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are more preferred.

[0059] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; and borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion.

[0060] The diazomethane derivative includes a compound represented by the following formula (B3). [ka]

[0061] In formula (B3), R 111 and R112 each independently represents an alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0062] The alkyl group may be linear, branched, or cyclic. Specific examples thereof include R 101 ~R 105 Examples of the halogenated alkyl group include the same as those exemplified in the description of 1. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group.

[0063] Examples of the aryl group which may have a substituent include a phenyl group, an alkoxyphenyl group such as a 2-, 3- or 4-methoxyphenyl group, a 2-, 3- or 4-ethoxyphenyl group, or a 3- or 4-tert-butoxyphenyl group, an alkylphenyl group such as a 2-, 3- or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group, and an aryl halide group such as a fluorophenyl group, a chlorophenyl group, or a 1,2,3,4,5-pentafluorophenyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0064] The glyoxime derivative includes a compound represented by the following formula (B4). [ka]

[0065] In formula (B4), R 121 ~R 124 are each independently an alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. 123 and R 124 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and when they form a ring, R123 and R 124 The group formed by bonding is a linear or branched alkylene group having 2 to 12 carbon atoms.

[0066] The alkyl group, the halogenated alkyl group, the aryl group which may have a substituent, and the aralkyl group include R 111 and R 112 Examples of the linear or branched alkylene group include an ethylene group, a propylene group, a butylene group, a hexylene group, and the like.

[0067] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, p-Toluenesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate sulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfonate dicyclohexylphenylsulfonium acid, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate,Examples of the sulfonium tetrakis(pentafluorophenyl)borate include triphenylsulfonium tetrakis(pentafluorophenyl)borate and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0068] Specific examples of the diazomethane derivative include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0069] Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis- Examples of the dimethylglyoxime include o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0070] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0071] Specific examples of the disulfone derivative include diphenyl disulfone and dicyclohexyl disulfone.

[0072] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0073] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0074] Specific examples of the imide-yl sulfonate derivative include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0075] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile.

[0076] Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and the like.

[0077] Specific examples of the triazine derivative include 2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(3,4-dimethoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine.

[0078] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0079] As the photoacid generator of the component (B), the above-mentioned onium salts and sulfonium salts are particularly preferred, with the above-mentioned sulfonium salts being more preferred.

[0080] The content of the photoacid generator (B) is preferably in the range of 0.05 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, based on the total amount of the photosensitive resin composition. When the photoacid generator is contained within the above range, a pattern with excellent resolution and excellent balance between sensitivity and developability during exposure without residual film can be obtained. The photoacid generator may be used alone or in combination of two or more kinds.

[0081] [(C) Quantum dots with specific surface coating layers] Quantum dots are nano-sized semiconductor materials. Atoms form molecules, and molecules form small molecular aggregates called clusters to form nanoparticles. When such nanoparticles show semiconductor properties, they are called quantum dots (quantum dot particles).

[0082] When a quantum dot receives energy from the outside and reaches an elevated state, it autonomously emits energy (emits light) according to the corresponding energy band gap.

[0083] The quantum dots (C) used in the present invention are not particularly limited as long as they have a surface coating layer containing siloxane, and can be used in any form. Quantum dots are mainly nanoparticles of 10 nm or less, but they may be nanowires, nanorods, nanotubes, nanocubes, etc., and any shape can be applied. In the present invention, the average particle size of the quantum dots was determined by directly observing at least 20 particles using a transmission electron microscope (TEM), calculating the diameter of a circle having the same area as the projected area of ​​the particle, and using the average value.

[0084] The quantum dots (C) used in the present invention can be made of any suitable material, for example, a semiconductor material selected from the group consisting of II-VI group, III-V group, IV group, IV-VI group, I-III-VI group, II-IV-V group, mixed crystals or alloys thereof, or compounds having a perovskite structure. Specific examples of compounds include, but are not limited to, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, Si, Ge, Sn, Pb, PbS, PbSe, PbTe, SnS, SnSe, SnTe, AgGaS2, AgInS2, AgGaSe2, AgInSe2, CuGaS2, CuGaSe2, CuInS2, CuInSe2, ZnSiP2, ZnGeP2, CdSiP2, CdGeP2, CsPbCl3, CsPbBr3, CsPbI3, CsSnCl3, CsSnBr3, and CsSnI3.

[0085] The quantum dots (C) used in the present invention can have a core-shell structure. The shell material capable of forming the core-shell structure is not particularly limited, but is preferably one having a large band gap and low lattice mismatch with respect to the core material, and can be arbitrarily combined according to the core material. Specific shell materials include ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BeS, BeSe, BeTe, MgS, MgSe, MgTe, PbS, PbSe, PbTe, SnS, SnSe, SnTe, CuF, CuCl, CuBr, CuI, etc., and the above materials may be selected as a single or multiple mixed crystals, but are not limited thereto.

[0086] There are various methods for producing the quantum dots (C) used in the present invention, such as a liquid phase method or a gas phase method, and the method is not particularly limited in the present invention. However, from the viewpoint of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained by a hot soap method or a hot injection method, in which a precursor species is reacted at high temperature in a nonpolar solvent with a high boiling point, and it is desirable that an organic ligand is coordinated to the surface in order to impart dispersibility in the nonpolar solvent and reduce surface defects.

[0087] From the viewpoint of dispersibility, the organic ligand preferably contains an aliphatic hydrocarbon. Examples of such organic ligands include oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, octanoic acid, oleylamine, stearyl (octadecyl)amine, dodecyl (lauryl)amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanethiol, trioctylphosphine, trioctylphosphine oxide, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, and tributylphosphine oxide, and the like, and these may be used alone or in combination.

[0088] In addition to the organic ligands, the (C) quantum dots used in the present invention are coordinated with ligands having a substituent capable of forming a siloxane bond. As the ligand having a substituent capable of forming a siloxane bond, it is preferable that the ligand has a substituent that interacts with or is adsorbed on the quantum dot surface. Examples of the substituent that interacts with or is adsorbed on the quantum dot surface include amino groups, thiol groups, carboxy groups, mercapto groups, phosphino groups, phosphine groups, phosphine oxide groups, sulfonyl groups, ammonium ions, and quaternary ammonium salts, among which amino groups, carboxy groups, mercapto groups, phosphine groups, and quaternary ammonium salts are preferred from the viewpoint of the strength of coordination.

[0089] The quantum dots (C) used in the present invention have a quantum dot surface coated with siloxane. Therefore, the ligand having a substituent that interacts with or adsorbs to the quantum dot surface has a substituent that can form a siloxane bond. Examples of the substituent that can form a siloxane bond include compounds containing alkoxysilanes such as trimethoxysilyl groups, triethoxysilyl groups, dimethoxymethylsilyl groups, diethoxymethylsilyl groups, dimethylmethoxysilyl groups, and ethoxydimethylsilyl groups, compounds having silazane bonds, compounds having Si-OH bonds, compounds having Si-X (X: halogen) bonds, and carboxylic acids. However, it is preferable to use ligands containing alkoxysilanes, silazane, and Si-OH because the reaction can proceed under mild conditions in which no acid is generated as a by-product of the reaction. Phenyl-containing siloxanes can be formed by reacting these with diphenyldisilanol or the like.

[0090] The amount of siloxane coated is not particularly limited, but is preferably in the range of 1 to 50 mass % of the quantum dots, and more preferably in the range of 5 to 30 mass %. If the amount of siloxane coated is too large, the quantum dot content decreases, but if it is within the above range, it is possible to improve dispersibility in the base polymer and suppress deterioration of the quantum dots during exposure.

[0091] The quantum dots (C) used in the present invention may further include a skeleton having a phenolic hydroxyl group in the surface coating layer.

[0092] The skeleton having a phenolic hydroxyl group is preferably a skeleton structure derived from the following formula (c). [ka]

[0093] In formula (c), Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 1 and R 2 R is each independently a hydrogen atom or a methyl group. 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 3 and a 4 are each independently an integer of 0 to 7, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. 3 and b 4 are each independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0094] The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, structural isomers thereof, etc. The alkoxy group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, structural isomers thereof, etc.

[0095] By introducing the skeletal structure of formula (c) into the surface coating layer, (A) the silicone resin having a phenolic hydroxyl group and the surface coating layer are crosslinked after exposure, which prevents the quantum dots from escaping during development and results in a pattern with high luminescence characteristics.

[0096] Furthermore, by introducing the skeletal structure of formula (c) into the surface coating layer, the compatibility with (A) the silicone resin having a phenolic hydroxyl group is improved, and the generation of aggregates when made into a photosensitive resin composition can be suppressed.

[0097] The content of the quantum dots (C) used in the present invention is preferably 5 to 80 mass % and more preferably 10 to 70 mass % based on the total amount of the photosensitive resin composition. If the content of the quantum dot particles is within the above range, fine patterns can be formed while maintaining good light emitting properties.

[0098] The method of introducing the phenolic hydroxyl group into the (C) component and the amount of introduction are not particularly limited, but a method of adding a previously prepared skeleton having an alkoxysilane-containing phenolic hydroxyl group and reacting it when forming the above-mentioned phenyl group-containing siloxane, or a method of directly introducing a skeleton having a phenolic hydroxyl group by radical reaction, etc. The amount of introduction may be appropriately adjusted in consideration of compatibility with the resin.

[0099] [(D) Crosslinking agent] The photosensitive resin composition of the present invention may further contain a crosslinking agent as component (D), which undergoes a condensation reaction with the phenolic hydroxyl group in the silicone resin (A) having a phenolic hydroxyl group, and is a component that facilitates the formation of a pattern and further increases the strength of the resin film after photocuring.

[0100] As the crosslinking agent, nitrogen-containing compounds containing two or more methylol groups and / or alkoxymethyl groups on average per molecule, such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having two or more methylol groups or alkoxymethyl groups on average per molecule, and epoxy compounds having two or more epoxy groups on average per molecule are also preferred. These compounds can be used alone or in combination of two or more.

[0101] The melamine compound may be one represented by the following formula (D1). [ka]

[0102] In formula (D1), R 201 ~R 206 are each independently a methylol group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and each molecule contains two or more methylol groups and / or alkoxymethyl groups on average. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0103] Examples of the melamine compound represented by the formula (D1) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0104] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying a melamine monomer with formaldehyde by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol, preferably a lower alcohol, for example an alcohol having 1 to 4 carbon atoms.

[0105] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0106] Examples of the glycoluril compound include tetramethylol glycoluril, tetrakis(methoxymethyl) glycoluril, etc. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, tetrapropoxymethyl urea, etc.

[0107] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0108] The modified melamine condensate may be obtained by addition condensation polymerization of a compound represented by formula (D1) or a multimer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. The addition condensation polymerization method may be a conventionally known method. The modified melamine represented by formula (D1) may be used alone or in combination of two or more.

[0109] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0110] The modified urea condensate can be obtained, for example, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation according to a known method, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0111] Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and the like.

[0112] Examples of the epoxy compound having two or more epoxy groups include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, triphenol alkane type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene-modified phenol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene ring-containing epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic type epoxy resins.

[0113] The content of the (D) component, when present, is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the (A) component. If the content of the (D) component is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation. The (D) component can be used alone or in combination of two or more types.

[0114] [(E) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (E). The solvent is not particularly limited as long as it can dissolve each of the above-mentioned components. By adding a solvent, the coatability of the photosensitive resin composition can be improved.

[0115] As such a solvent, organic solvents are preferred because they have excellent solubility for these components. Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have excellent solubility for photoacid generators.

[0116] From the viewpoints of compatibility and viscosity of the photosensitive resin composition, the content of the component (E) is preferably from 25 to 85 mass %, and more preferably from 35 to 75 mass %, based on the total amount of the photosensitive resin composition.

[0117] [Photosensitive resin film] The photosensitive resin film of the present invention is a dried product of the above-described photosensitive resin composition.

[0118] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) applying the above-described photosensitive resin composition onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. Includes.

[0119] Step (i) is a step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin film on the substrate, such as a silicon wafer, a glass wafer, a quartz wafer, a micro LED laminate substrate, etc.

[0120] The coating method may be a known method, such as a dipping method, a spin coating method, a roll coating method, etc. The coating amount can be appropriately selected depending on the purpose, but it is preferable to coat the resulting photosensitive resin film so that the film thickness is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0121] In order to improve the film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dropped can be appropriately selected depending on the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as propylene glycol monomethyl ether, etc. are preferable, but it is also possible to use a solvent used in the photosensitive resin composition.

[0122] Here, in order to efficiently carry out the photocuring reaction, the solvent and the like may be evaporated in advance by preheating (prebaking) as necessary. Prebaking can be carried out, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0123] Next, (ii) the photosensitive resin film is exposed to light. In this case, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, and more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line, h-line, and i-line, and far ultraviolet light (248 nm, 193 nm). Of these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 is preferred.

[0124] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out. The material of the photomask is not particularly limited, but is preferably a material that blocks light of the wavelength. For example, a photomask having chromium as a light-shielding film is preferably used, but is not limited thereto.

[0125] Furthermore, in order to increase the development sensitivity, a post-exposure bake (PEB) may be performed. PEB is preferably performed at 40 to 150°C for 0.5 to 20 minutes. The exposed portion is crosslinked by PEB to form an insolubilized pattern that is insoluble in an organic solvent, which is a developer. The product is left in a dry state after the solvent is removed through this pre-baking.

[0126] (iii) After exposure or PEB, the substrate is developed with a developer to dissolve and remove the non-exposed areas to form a pattern. As the developer, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether are preferred, but it is also possible to use solvents used in photosensitive resin compositions. As the development method, a conventional method, for example, a method of immersing a substrate on which a pattern has been formed in the developer, can be mentioned. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a cured film having a desired pattern.

[0127] Furthermore, the film on which the pattern is formed may be post-cured, preferably at 100 to 200° C., using an oven or a hot plate.

[0128] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating obtained from a photosensitive resin composition on the support film.

[0129] The photosensitive dry film (support film and photosensitive resin film) is solid, and since the photosensitive resin film does not contain a solvent, there is no risk of bubbles caused by the volatilization remaining inside the photosensitive resin film and between the film and the substrate having irregularities. The thickness of the photosensitive resin film is not particularly limited, but is preferably 1 to 200 μm, and more preferably 3 to 100 μm.

[0130] In addition, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity in an appropriate viscosity range, and can penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the viewpoint of the fluidity of the photosensitive resin film, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120° C. In addition, the viscosity in the present invention is a value measured by a rotational viscometer.

[0131] When the photosensitive dry film of the present invention is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin composition of the present invention is characterized by its softening performance, and therefore can achieve even higher flatness. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps between the substrate and the photosensitive resin film can be more effectively prevented.

[0132] The photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film. As a production device for the photosensitive dry film, a film coater for producing a pressure-sensitive adhesive product can be used. Examples of the film coater include a comma coater, a comma reverse coater, a multi-coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-bottom reverse coater, and a four-bottom reverse coater.

[0133] When the support film is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater, the photosensitive resin composition is applied to the support film in a predetermined thickness, and then the film is passed through a hot air circulating oven at a predetermined temperature and time, and dried on the support film to form a photosensitive resin film, thereby producing a photosensitive dry film. In addition, if necessary, the photosensitive dry film is passed through a laminating roll at a predetermined pressure together with a protective film unwound from another unwinding shaft of the film coater to bond the photosensitive resin film on the support film to the protective film, and then the film is wound up on the winding shaft of the film coater to produce a photosensitive dry film with a protective film. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0134] The support film used in the photosensitive dry film of the present invention may be a single-layer film made of a single film, or a multi-layer film made of a laminate of multiple films. Examples of the material of the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate, which has appropriate flexibility, mechanical strength, and heat resistance, is preferred. These films may be subjected to various treatments such as corona treatment and release agent coating. These may be commercially available products, such as Therapeel WZ (RX), Therapeel BX8 (R) (all manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (all manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (all manufactured by Teijin DuPont Films Co., Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Corporation).

[0135] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene having appropriate flexibility are preferred. Commercially available products may be used, and examples of the polyethylene terephthalate include those already exemplified, and examples of the polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nippa Co., Ltd.).

[0136] The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of curling around the core.

[0137] [Patterning method using photosensitive dry film] The pattern forming method using the photosensitive dry film of the present invention includes the steps of: (i') attaching the photosensitive resin film of the photosensitive dry film described above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. Includes.

[0138] First, (i') a photosensitive dry film is used to attach the photosensitive resin film onto a substrate, thereby forming a photosensitive resin film on the substrate. That is, the photosensitive resin film of the photosensitive dry film is attached to the substrate, thereby forming a photosensitive resin film on the substrate. In addition, when the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is attached to the substrate. The attachment can be performed, for example, by using a film attachment device.

[0139] The film laminating device is preferably a vacuum laminator. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature in a vacuum chamber at a predetermined vacuum level using a laminating roll at a predetermined pressure. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0140] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as necessary. Pre-baking can be performed, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0141] As in the case of the pattern forming method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer and dissolving and removing the non-exposed parts to form a pattern, and (iv) performing a post-curing heat treatment as necessary. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods depending on the process.

[0142] By the pattern forming method using the photosensitive resin composition or photosensitive dry film of the present invention, fine pattern formation can be easily performed. For example, the photosensitive resin composition or photosensitive dry film of the present invention is formed so as to cover a large number of blue micro LEDs arranged on a substrate, and then a fine pattern is formed to form a cured film containing red or green quantum dots on each part of the blue micro LED, which can also emit red or green light, making it possible to produce a full-color light-emitting device.

[0143] [Light emitting element] The light-emitting device of the present invention is provided with a cured coating film obtained by the above-described pattern formation method. EXAMPLES

[0144] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. Note that InP / ZnSe / ZnS core-shell quantum dots are used as quantum dot materials, and the core synthesis method is as shown in [1-1] (red quantum dots) and [1-2] (green quantum dots) described later, and the subsequent shell synthesis method is as shown in [2].

[0145] [1-1] Red quantum dot core synthesis process Two flasks were prepared, and 0.23g (0.9mmol) of palmitic acid, 0.088g (0.3mmol) of indium acetate, and 10mL of 1-octadecene were added to each flask. The mixture was heated and stirred at 100℃ under reduced pressure, and degassed for 1 hour while dissolving the raw materials. Nitrogen was then purged into the two flasks, and 0.75mL (0.15mmol) of tristrimethylsilylphosphine / trioctylphosphine solution (0.2M) was added to both flasks. One flask was then heated to 300℃, and the solution was removed from the flask that was not heated and added to the flask heated to 300℃, producing core particles.

[0146] [1-2] Green quantum dot core synthesis process 0.23g (0.9mmol) of palmitic acid, 0.088g (0.3mmol) of indium acetate, and 10mL of 1-octadecene were added to the flask, and the mixture was heated and stirred at 100℃ under reduced pressure to dissolve the raw materials and degassed for 1 hour. After that, nitrogen was purged into the flask, and 0.75mL (0.15mmol) of a 0.2M solution of tristrimethylsilylphosphine and trioctylphosphine was added and the temperature was raised to 300℃ to generate core particles.

[0147] [2] Quantum dot shell layer synthesis process Next, 2.85g (4.5mmol) of zinc stearate and 15mL of 1-octadecene were added to another flask, and the mixture was heated and stirred at 100°C under reduced pressure. While dissolving, the mixture was degassed for 1 hour to prepare a 0.3M zinc stearate octadecene solution. 3.0mL (0.9mmol) was added to the reaction solution after the core synthesis and cooled to 200°C. Next, 0.474g (6mmol) of selenium and 4mL of trioctylphosphine were added to another flask, and the mixture was heated to 150°C and dissolved to prepare a 1.5M selenium trioctylphosphine solution. The reaction solution after the core synthesis step, which had been cooled to 200°C, was heated to 320°C over 30 minutes, and the selenium trioctylphosphine solution was added in 0.1mL increments to a total of 0.6mL (0.9mmol), and the mixture was held at 320°C for 10 minutes and then cooled to room temperature. 0.44g (2.2mmol) of zinc acetate was added and dissolved by heating and stirring at 100℃ under reduced pressure. The flask was purged again with nitrogen and heated to 230℃, and 0.98mL (4mmol) of 1-dodecanethiol was added and held for 1 hour. The resulting solution was cooled to room temperature to produce a core-shell quantum dot-containing solution. The red core-shell quantum dots synthesized through steps [1-1] to [2] were designated R-1, and the green core-shell quantum dot-containing solution synthesized through steps [1-2] to [2] were designated G-1.

[0148] [3] Ligand exchange process (3-mercaptopropyl)triethoxysilane was used as a ligand having a substituent capable of forming a siloxane bond and a substituent that coordinates to the quantum dot surface. For the ligand exchange reaction, (3-mercaptopropyl)triethoxysilane (3.0 mmol) was added to the solution after the shell synthesis process that had been cooled to room temperature and stirred for 24 hours. After the reaction was completed, ethanol was added to precipitate the reaction solution, which was then centrifuged and the supernatant was removed. The same purification was performed again, and the solution was dispersed in toluene to prepare a quantum dot solution in which a ligand having a substituent capable of forming a siloxane bond was coordinated. The quantum dots synthesized using R-1 and R-2 were used to coordinate a ligand having a substituent capable of forming a siloxane bond, and the quantum dots synthesized using G-1 and G-2 were used to coordinate a ligand having a substituent capable of forming a siloxane bond.

[0149] [4-1] Surface coating layer formation process Triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after the ligand exchange process were added to a flask that had been purged with nitrogen, and the mixture was heated and stirred at 65°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, ethanol was added to precipitate the reaction solution, and the mixture was centrifuged to remove the supernatant. The mixture was dispersed in toluene and added to a flask that had been purged with nitrogen in advance, and 2 parts by mass of the compound represented by the following formula (1) and the quantum dot toluene solution were added per 100 parts by mass. Furthermore, 1 part by mass of Irgacure 1173 was added per 100 parts by mass of the compound represented by the following formula (1), and after stirring and mixing, the mixture was irradiated with a UV LED irradiation device at a wavelength of 365 nm and an output of 4000 mW / cm. 2 The mixture was irradiated with light for 20 seconds. After the reaction was completed, ethanol was added to cause precipitation, and after centrifugation, the supernatant was removed and the mixture was dispersed in toluene again. PGMEA was then added, and the toluene solvent was removed by vacuum distillation to produce a quantum dot solution with a surface coating layer (a solution with a solid content of 60%). Here, the quantum dots with a surface coating layer formed based on R-2 are called R-(1), and the quantum dots with a surface coating layer formed based on G-2 are called G-(1).

[0150] [4-2] Surface coating layer formation process Triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after the ligand exchange process were added to a flask that had been purged with nitrogen, and the mixture was heated and stirred at 65°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, ethanol was added to precipitate the reaction solution, and the mixture was centrifuged to remove the supernatant. The mixture was dispersed in toluene and added to a flask that had been purged with nitrogen in advance, and 2 parts by mass of the compound represented by the following formula (1') and the quantum dot toluene solution were added per 100 parts by mass. Furthermore, 1 part by mass of Irgacure 1173 was added per 100 parts by mass of the compound represented by the following formula (1'), and after stirring and mixing, the mixture was irradiated with a UVLED irradiation device at a wavelength of 365 nm and an output of 4000 mW / cm. 2 The mixture was irradiated with light for 20 seconds. After the reaction was completed, ethanol was added to cause precipitation, and after centrifugation, the supernatant was removed and the mixture was dispersed in toluene again. PGMEA was then added, and the toluene solvent was removed by vacuum distillation to produce a quantum dot solution with a surface coating layer (a solution with a solid content of 60%). Here, the quantum dots with a surface coating layer formed based on R-2 are designated R-(1'), and the quantum dots with a surface coating layer formed based on G-2 are designated G-(1').

[0151] [5] Synthesis of silicone resin [Synthesis Example 1] Synthesis of Resin 1 A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser was charged with 215.0g (0.50 mol) of compound (1), followed by 2,000g of toluene, and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was charged, and 58.2g (0.30 mol) of compound (2) and 604.0g (0.20 mol) of compound (4) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain resin 1. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 1 to be 80,000 (silicone content was 68.9% by mass: silicone content was calculated from the amount charged).

[0152] [Synthesis Example 2] Synthesis of Resin 2 A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser was charged with 215.0g (0.50 mol) of compound (1), followed by 2,000g of toluene, and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was charged, and 67.9g (0.35 mol) of compound (2) and 6.7g (0.05 mol) of compound (3), and 302.0g (0.10 mol) of compound (4) were dropped over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain resin 2. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 2 to be 40,000 (silicone content was 52.2% by mass).

[0153] [Synthesis Example 3] Synthesis of Resin 3 A 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 215.0g (0.50 mol) of compound (1), followed by 2,000g of toluene, and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was charged, and 87.3g (0.45 mol) of compound (2) and 6.7g (0.05 mol) of compound (3), and 151.0g (0.05 mol) of compound (4) were dropped over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain resin 2. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 3 to be 13,000 (silicone content was 34.3% by mass).

[0154] The compounds (1) to (4) used in the above synthesis examples are as follows. [ka]

[0155] [6] Preparation and evaluation of photosensitive resin composition [Examples 1 to 12 and Comparative Examples 1 to 24] Each component was blended according to the blending amounts shown in Tables 1 to 4, then stirred and mixed at room temperature and microfiltered through a 1.0 μm glass filter to obtain photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 24.

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] [Table 4]

[0160] In Tables 1 to 4, the photoacid generators B-1 and B-2 used are as follows. [ka]

[0161] In Tables 1 to 4, the crosslinking agents D-1 and D-2 used are as follows. [ka]

[0162] In Tables 1 to 4, the quantum dots R-3 are S-BE030 manufactured by Shoei Chemical Co., Ltd. (particle size 5 to 10 nm, material InP:ZnS:SeZn = 25:50:25), R-4 are 900514-1ML manufactured by Aldrich (particle size 5 to 10 nm, material CdSe (core) / CdS (shell) core-shell type), G-3 are S-BE029 manufactured by Shoei Chemical Co., Ltd. (particle size 3 to 5 nm, material InP:ZnS:SeZn = 25:50:25), and G-4 are 900511-1ML manufactured by Aldrich (particle size 3 to 5 nm, material CdSe (core) / CdS (shell) core-shell type).

[0163] [7] Preparation of photosensitive dry film Using a die coater as a film coater and a polyethylene terephthalate film (thickness 38 μm) as a support film, the photosensitive resin compositions listed in Tables 1 to 4 were applied onto the support film. Next, the film was dried by passing through a hot air circulating oven (length 4 m) set at 100° C. for 5 minutes to form a photosensitive resin film on the support film to a thickness of 20 μm, thereby obtaining a photosensitive dry film. A polyethylene film (thickness 50 μm) was attached as a protective film to the photosensitive resin film using a laminating roll at a pressure of 1 MPa to produce a photosensitive dry film with a protective film.

[0164] [8] Evaluation of photosensitive resin coating (1) Confirmation of aggregates in the photosensitive resin film The protective film was peeled off from the photosensitive dry film with the protective film, and aggregates in the photosensitive dry film were confirmed using an optical microscope. Aggregates with a size of 1 μm or more were marked with an X, and aggregates with no aggregates or with a size of less than 1 μm were marked with an O. The results are shown in Tables 5 to 8.

[0165] (2) Pattern formation and its evaluation The photosensitive dry film with the protective film was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to the silicon wafer. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, in order to enhance adhesion to the substrate, pre-baking was performed on a hot plate at 110°C for 3 minutes. In order to form a square island pattern with a pitch width of 1:1 with the adjacent pattern through a mask on the obtained photosensitive resin film, exposure was performed using an i-line stepper NSR-2205i11D (manufactured by Nikon Co., Ltd.). After irradiation, PEB was performed on a hot plate at 120°C for 3 minutes, and then cooled, and the substrate was spray-developed with PGMEA for 60 seconds to form a pattern. Then, the substrate was post-cured using an oven at 150°C for 2 hours while purging with nitrogen. Then, the formed island patterns with sides of 100 μm, 50 μm, 30 μm, 20 μm, and 10 μm were observed with a scanning electron microscope (SEM), and the smallest pattern size that was not connected to the adjacent island pattern (pitch width 1:1) was determined as the limiting resolution. In addition, those in which the resolution did not reach 100 μm or the pattern peeled off during development were determined as ×. The results are shown in Tables 5 to 8.

[0166] (3) Evaluation of the luminescence properties of the formed patterns Using LabRAM HR Evolution manufactured by Horiba Techno Service Co., Ltd., the patterned sample prepared in (2) above was irradiated with 457 nm laser light (0.03 mW), the photoconverted island pattern area was measured, and the emission intensity, emission wavelength, and half-width of the photoconverted light were measured. In addition, the sample prepared in (2) above after the lamination and support film peeling process was similarly measured to measure the emission intensity of the photoconverted light. The results are shown in Tables 5 to 8 (M: million).

[0167] (4) Reliability test evaluation A glass substrate was coated with the photosensitive resin composition shown in Tables 1 to 4 in a thickness of 100 μm using a spin coater. In order to remove the solvent from the composition, the substrate was placed on a hot plate and dried by heating at 110° C. for 20 minutes. In order to form a square island pattern with a side length of 1 cm on the obtained photosensitive resin film through a mask, the film was exposed using a contact aligner type exposure device under exposure conditions of 365 nm. After irradiation, PEB was performed on a hot plate at 140° C. for 5 minutes, and then cooled, and the substrate was spray-developed with PGMEA for 300 seconds to form a pattern. Then, the substrate was post-cured in an oven at 150° C. for 2 hours while purging with nitrogen. The patterned sample was subjected to a heat cycle test (1,000 cycles of holding at -55° C. for 10 minutes and holding at 125° C. for 10 minutes were repeated), and the peeling state of the cured film from the substrate after the heat cycle test and the presence or absence of cracks were confirmed. Those that showed no peeling or cracking were marked with an ◯, and those that showed even one peeling or cracking were marked with an X. The results are shown in Tables 5 to 8.

[0168] [Table 5]

[0169] [Table 6]

[0170] [Table 7]

[0171] [Table 8]

[0172] The above results demonstrate that the photosensitive resin composition of the present invention can form a good photosensitive coating or photosensitive dry film free of aggregates (or if any, the aggregates are extremely small), and can provide a cured coating having high lithography resolution, high luminescence characteristics that do not change before and after the lithography process, and good reliability (adhesion and crack resistance), which is suitable for light-emitting devices.

[0173] The present specification includes the following aspects. [1]: A photosensitive resin composition comprising: (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane. [2]: The photosensitive resin composition according to the above [1], wherein the component (C) contains a skeleton having a phenolic hydroxyl group in the surface coating layer. [3]: The photosensitive resin composition according to the above [1] or [2], characterized in that the component (A) contains a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1): [ka] [In the formula, R 5 ~R 8 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 0 to 600. X 1 is a divalent group represented by the following formula (X1). [ka] (In the formula, Y 1R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 9 and R 10 R is each independently a hydrogen atom or a methyl group. 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 are each independently an integer of 0 to 7. 1 and b 2 are each independently an integer of 0 to 2.)] [4]: The photosensitive resin composition according to [1], [2] or [3] above, further comprising, as a component (D), at least one crosslinking agent selected from the group consisting of melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups in one molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups in one molecule. [5]: The photosensitive resin composition according to [1], [2], [3] or [4], characterized in that the quantum dots of component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion. [6]: The photosensitive resin composition according to [1], [2], [3], [4] or [5], wherein the component (C) is contained in an amount of 5 to 80 mass % in the photosensitive resin composition. [7]: The photosensitive resin composition according to [1], [2], [3], [4], [5] or [6] above, further comprising (E) a solvent. [8]: A photosensitive resin film, which is a dried product of the photosensitive resin composition according to [1], [2], [3], [4], [5], [6] or [7]. [9]: A photosensitive dry film comprising a support film and the photosensitive resin coating of [8] above on the support film.

[10] : A pattern forming method, comprising the steps of: (i) applying the photosensitive resin composition of the above [1], [2], [3], [4], [5], [6] or [7] onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. A pattern forming method comprising the steps of:

[11] : A pattern forming method comprising the steps of: (i') a step of attaching the photosensitive resin film of the photosensitive dry film [9] above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. A pattern forming method comprising the steps of:

[12] : A light-emitting device comprising a cured coating obtained by the pattern formation method according to

[10] or

[11] above.

[0174] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A photosensitive resin composition comprising: (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (C) contains a skeleton having a phenolic hydroxyl group in the surface coating layer.

3. 3. The photosensitive resin composition according to claim 1, wherein the component (A) contains a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1): 【Chemistry 1】 [In the formula, R ５ ~R ８ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 0 to 600. １ is a divalent group represented by the following formula (X1). 【Chemistry 2】 (In the formula, Y １ R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. ９ and R １０ R is each independently a hydrogen atom or a methyl group. １１ and R １２ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. １ and a ２ are each independently an integer from 0 to 7. １ and b ２ are each independently an integer of 0 to 2.

4. 4. The photosensitive resin composition according to claim 1, further comprising, as component (D), at least one crosslinking agent selected from the group consisting of melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups in one molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups in one molecule.

5. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that the quantum dots of the component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (C) is contained in the photosensitive resin composition in an amount of 5 to 80% by mass.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a solvent.

8. A photosensitive resin film, which is a dried product of the photosensitive resin composition according to any one of claims 1 to 7.

9. A photosensitive dry film comprising: a support film; and the photosensitive resin film according to claim 8 on the support film.

10. A pattern formation method comprising the steps of: (i) applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. A pattern forming method comprising the steps of:

11. A pattern formation method comprising the steps of: (i') a step of attaching the photosensitive resin film of the photosensitive dry film according to claim 9 onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed areas to form a pattern. A pattern forming method comprising the steps of:

12. A light-emitting device comprising a cured film obtained by the pattern formation method according to claim 10 or 11.